JPS59166956A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain fastness and superior solubility in high boiling solvents by incorporating a specified cyan dye forming coupler. CONSTITUTION:A cyan dye forming coupler is represented by formula I in which R1 is H, halogen, 1-20 conductive substrate chain alkyl or alkoxy; R2 is 1-20C alkyl; R3 is H, halogen, or alkyl; X is a group releasable on the oxidation coupling with a developing agent; and (a) is 1 or 2. This coupler is easily prepd. from a compd. of formula II synthesized from cheap phenol and a compd. of formula III synthesized from 2-aminp-5-nitrophenol deriv. A silver halide photosensitive material contg. this coupler is imagewise exposed and color developed, and at that time, the coupler reacts with an oxidized developing agent of aromatic primary amine to form a color image. The coupler is high in the dye forming speed and the max. color developing density in a color developing soln., and it remains high enough even in the color developing soln. excluding benzyl alcohol. Deterioration of color density is found little even when said material is processed with a bleaching soln. weak in oxidation power.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photographic material (1) containing a novel cyan dye-forming coupler.

After the silver halide photographic material is exposed to light, color development is performed, whereby the oxidized aromatic-amine developing agent reacts with the dye-forming coupler to form a color image. Generally, in this method, a hypsochromic color reproduction method is used (in order to reproduce blue, green, and red, blue, green, and red are complementary colors, respectively), and low, magenta, and cyan color images are formed. Ru.

Phenols and naphthols are often used as cyan image forming agents. However, there remain several problems with the preservation of color images obtained from conventionally used phenols and naphthols.

An example is U.S. Patent 2, 367.

! 3/and 2, the color images obtained from the two-acylaminophenolic cyan couplers described in '723.730 generally have poor heat fastness, and US Pat.
The color images obtained from the J''-diacylaminophenolic cyan couplers described in J'', Kota and Ko, No. 772,762 generally have poor light fastness; , generally poor in both light and heat fastness.

On the other hand, U.S. Patent No. 396 and Japanese Patent Application
/, f! t, No. 637, JP-A-Shoj7-/37°, 24t
, λ, which is stated in the specification such as < issue,! -Diacylaminophenol cyan coupler is said to have superior robustness and good solubility in high boiling point organic solvents compared to the general cyan couplers mentioned above, but it is not at a fully satisfactory level and can be stored for a long time. □
It has the disadvantage that it tends to crystallize when added to photographic emulsions, and the phenol used to synthesize ballast groups by reacting with α-octacolocarboxylic acid or ester is not commercially available. Requires numerous synthetic reactions,
Therefore, it has the disadvantage that the coupler becomes expensive.

The object of the present invention is to overcome these drawbacks and provide a color photographic material using a cyan dye-forming coupler that is robust and easily soluble in high-boiling organic solvents.

Another object of the present invention is to provide a coupler which has a high rate of dye formation and a maximum color density in a color developer, and in particular has a high dye formation rate and a high maximum color density even in a color developer excluding benzyl alcohol. It is an object of the present invention to provide a coupler at a low cost that shows almost no decrease in concentration even when treated with a bleaching solution having weak oxidizing power or a bleaching solution that is exhausted.

The object of the present invention is achieved by a coupler represented by the following general formula [■].

General formula [1] In general formula CII, R1 is a hydrogen atom, a halogen atom (
(e.g., fluorine atom, chlorine atom, bromine atom, etc.), or chain alkyl groups (e.g., methyl, ethyl, butyl, etc.) having carbon number/-20, or alkoxy groups (e.g., methoxy, ethoxy, tetradecyl). (oxy group, etc.)
The substitution position may be the ortho position, the meta position, or the ξ position.

In the general formula [1], R2 represents an alkyl group having carbon number/-10 (eg, methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, etc.).

In the general formula [I:N2, R3 represents a hydrogen atom, a halogen atom (for example, a chlorine atom, etc.), or an alkyl group (for example, a methyl group, -xyl group). In [-General formula T], X is a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), and the leaving group represented by group, carboxymethoxy group, methylsulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, naphthyloxy group, glucarboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetrazocatyloxy group, benzoyl group) oxy group, etc.), sulfonyloquine group (e.g., Eva, methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (e.g., dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group) etc.), alkoxycarbonyloxy groups (eg, ethoxycarbonyloxy &, etc.), aryloxycarbonyloxy groups (eg, phenoxycarbonyloxy groups, etc.), and imide groups (eg, succinimide groups, hydantoyl groups, etc.).

In the general formula [I)E, n represents/or the number of pots.

In general formula 1), preferred R1 is a hydrogen atom, a halogen atom, a methyl group, or a methoxy group.

In the general formula [■], the substitution position of <R1 excluding the hydrogen atom is preferably the ortho position.

In the general formula CITE, the preferred number of carbon atoms in R2 is θ
It is.

In general formula [T), R3 is preferably a hydrogen atom, a halogen atom, or a methyl group, more preferably a hydrogen atom or a chlorine atom, and a hydrogen atom is particularly preferred.

In the general formula [I:H2, preferred X is a hydrogen atom or a chlorine atom.

In general formula (I), preferred n is /.

The following (2) typical examples of couplers included in the present invention are listed below, but the couplers of the present invention used in the present invention are not limited to these.

(1) α of α The coupler of the present invention is synthesized by the method shown below (2).

/ That is, the compound [Al is synthesized by the reaction shown in the above formula using an easily available and inexpensive phenol represented by the general formula CI), while co-amino! The coupler of the present invention represented by the general formula [I] can be synthesized by reaction with a reduced form of compound (B) synthesized from a -ditrophenol derivative.

Next, a specific synthesis example is shown below.

Synthesis Example/2 Synthesis of Exemplary Coupler (,2) 1) Compound [A
) (R3=H) synthesis of orthochlorophenol λθ, 3? and ethyl α-promotetradecanoate S/, V to dimethylformamide 7? 02 was added to anhydrous potassium carbonate 2, and the mixture was heated and stirred on a steam bath for 2 hours. After cooling, ethyl acetate was added and water washing was performed twice. After distilling off the solvent under reduced pressure, add methanol/, :zomil and sodium hydroxide, 3 g to water/! ml of the solution was added, and the mixture was heated and stirred for 7 hours.

After cooling, add 0m7 of water, make it acidic with hydrochloric acid, and remove the precipitated crystals to obtain the melting point! ~g3°C crystal at i+2.39
Obtained. This crystal Y♂, 39 is converted into benzene J' t m, d
After stirring, thionyl chloride/ml was added dropwise under heating under reflux, and the mixture was heated under reflux for 7 hours. Excess reagent was distilled off under reduced pressure to obtain JM compound (Al (R3=8) 29).

I) Synthesis of Exemplary Coupler (2) Tuamino-goo-chloro! -nitrophenol37.
2fj was suspended in acetonitrile 20θmzt2 and O-chlorobenzoyl chloride 3s, g y was heated under reflux.
was added dropwise over 7 hours, and the mixture was further heated under reflux for 7 hours. After cooling, the crystals were removed to obtain Compound CB] j31.

Is the compound [B) obtained here converted into reduced iron 3? , ammonium chloride 37, isopropanol/Otθrnll.

After cooling, sodium hydroxide/4t7 was dissolved in water (70m7+) to obtain iron powder, which was then neutralized with acetic acid. The precipitated crystals were collected in an oven and dried. This crystal, 232, was suspended in 700 ml of acetonitrile, and the uncompound [:Alzy] was added dropwise under heating and reflux.

After the dropwise addition, the mixture was stirred under reflux for 7 hours and then cooled to obtain crystals. Ethyl acetate! θmll.

Recrystallize from 720 ml of acetonitrile to obtain the exemplary coupler (F) with melting point //~//j0C at 29. /v got it.

The example couplers can also be synthesized by a similar method.

The melting points of typical couplers are shown below.

(1) / , 2 /-/ J 3°C, (4) / θ
Gu/θg'c, (5) io Doug-0 Otsu 0CX (1
1) Photographic emulsion made using the present invention (- may contain a color image-forming coupler other than the present invention. The coupler is
- A non-diffusing one having a hydrophobic group called a balanute group is desirable. The coupler may be either g-equivalent or di-equivalent to the silver ion.

It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor (so-called DIR coupler).

The coupler may be such that the product of the coupling reaction is colorless.

Ren couplers can be used. Among these, benzo-f-acetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used are given in U.S. Patent No. 2. ,! ? 7J-.

θ! No. 7. 3.26! , jθ. Same 3. RiO♂,
No. 729. Same 3. jr o/, /j! No. 3゜Jrr2
．． No. 32.2. J', 7.2j, No. 672, No. 3, ♂ri/, No. 775. West German patent i, s gua,? No. 2, West German Application Publication No. -2/9, No. 9/7, No. λ, 2t/, No. 3t7, No. 4t/g, No. θθ, British Patent/, No. ¥23.0.20 , Tokuko Shoj/-10? ?
No. 3, No. 733 in JP-A No. 4t7-2, same 4t? -73/
No. 2, same j/-102, No. 36, same jO-t3 g/No., same O θ-/233Y, No. 2, same! 0-/3θ Kuda No. 2, same j/-2/ and +27, same jθ-I7 Otsu! θ, same! Ko and 2g 2g issue, same! --//Oko No. 79, etc.

As the magenta coloring coupler, pyrazolone compounds can be used, and pyrazolone compounds are particularly advantageous. A specific example of a magenta color-forming coupler that can be used is disclosed in U.S. Patent λ, 00,7♂? No., same, 973, ZaO/No., same 3, 01. ．． 2. Otsu! No. 3, same 3. /, 27.
2nd issue, 3', 3//, 2nd issue, 3rd. G/
ri, No. 39/3. ．． f/9゜729, same 3. ! evening! , 3/ri issue, same 3. Ta? Ko, No. 322, 3, t/
! ,! Ot issue, same 3゜? 3g, 90? No. 3J/
, No. 791, West German patent/,! '10. Rizada, West German patent application (OLS) 2,4t0r2g No. 1, West German patent application (OLS) 2,47
/7,9g No. 1, same co, g/l? , No. 962, same co, g2g.

ri No. 67, Tokuko Shogu θ-6037, Tokukai Sho S/--〇/26, same! Ko! ? No. 922, Getter/29!3
No. f, No. 49-741027, No. 0-7!933g
No. 62-/Lt2/, No. 2/, No. 419-74t0
2t! ? No. 5O-t0233, O/-243g/No. 1. This is what is described in the 3-J Ta/Coco issue, the same, etc.

As the cyan coloring coupler, phenolic compounds, naphthol compounds, etc. can be used. Specific examples include U.S. Patent λ, 3t9.929, US Pat.
27. No. 2, same, g7g, tips No. 3, same, 2. ! Ko/
, 90! No. 2. and 9t, and 2nd issue, 3.03g,
cr9.2, same 3,3//.

Gua ni issue, same 3. Geta and 3 No. 3. Gua g, 1
Go No. 3, same 3. ! ? 3.97/issue, same 3゜! ri/ , 3
T3 issue, same 3I7 go 7.9! // issue, same number, θb4t,
9. :zq, West German patent application (OLS), gu/
4t! No. 30, same, ri! Gua No. 329, Japanese Patent Publication No. 4J
? -39 and 3, same number 4/-2, number 03, same number/-
! 0! , No., same j/-/g1. ! ? No. 2J', No. 902T, No. 90232 (:).

As a colored coupler, for example, the US patent 3°g 2g
,! gQ issue, same...! 2/, 9θ and 3, θ3g, ? No. 92, Special Public Sho Doug No. 2076, No. 3♂--, 2
No. 33j, same Guko / No. 13041, same Taku 324
tl / issue, specification No. 037 in JP-A Showo/-2, JP-A No. 32
-412/2/Specification, West German Patent Application (OLS), 2
,4t/and,9! You can use the ones listed in No.

D[, R couplers include, for example, U.S. Pat.
．． 27. tj gu issue, same 3. t/7. λ9/No. 3.7
0/, 7t3, 3,790,3. ! ? Z No. 3,
632,3 guj, West German patent application (OT, S) ko, gu/
gu, oo otsu issue, same co, gu jl, 3θ/ issue, same λ, rij
No. 3.29, British Patent 9!3. Guogu, JP-A-5
Those described in No. t9d24, No. 4t9-72233j, and Tokuko Shoj/-/J/g/ can be used.

In addition to the DIR coupler (2), the light-sensitive material may contain a compound that releases a development inhibitor upon development; for example, U.S. Pat.
No. 29, West German Patent Application (Or, 8) 21/7. Issue ri/4, Tokukai Sho! Ko/lko 2/issue, Tokukai Sho Doug-9
Those described in No. 714 can be used.

The coupler of the present invention may contain two or more types of the above-mentioned couplers (=same layer C).The same compound may be contained in two or more different layers.

The couplers of the present invention are generally added in an amount of .lambda..times./.theta.-3 mol to j.times.10" mol, preferably /.times./.theta.-2 mol to !XIO" mol per 7 mol of silver in the two emulsion layers.

The above-mentioned couplers can be introduced into the silver halide emulsion layer by known methods, such as U.S. Pat. No. 2,322.

The method described in No. 027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, trinoenyl phonophate, tric 1
citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. dietheracrylamide), fatty acid esters (e.g. dibutoxy ethyl succinate, dioctyl azelate), phenols (e.g., co-, tert-amylphenol), etc., or organic solvents with a boiling point of about 30 °C to /1o0C, such as lower alkyl acedates such as ethyl acetate, butyl acetate, etc. After dissolving in ethyl propionate, -a-class-it alcohol, methyl [butyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc.], it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also, special public Akiko / -39 and Yu 3, special public Akiko / -j ri 9
The dispersion method using polymers described in Section 3 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it becomes hydrophilic as an alkaline aqueous solution: r L
It is introduced during the 1st id.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzito9azole compounds substituted with aryl groups (e.g. those described in U.S. Pat.
Same 3,3o λ.

3), benzophenone compounds (for example, those described in JP-A-4T4-.27J'g),
Cinnamate ester compounds (for example, US patent 3°7θ!
, and those described in No. 05 and No. 3.707.37j),
sitadiene compounds (e.g. U.S. patents Gu, Og!, 2.
29) or benzoxyzole compounds (for example, those described in US Pat. No. 3.7θθ, Guj!) can be used. Furthermore, US Patent 3. 9
9,762, JP-A-Sho J Google J', (-36) may also be used. These ultraviolet absorbers may be mordanted in a specific layer.

For the purpose of increasing sensitivity, increasing contrast, or promoting development, the photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary It may also contain ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US patent ko, gu0θ,! No. 32, same, g λ3. ! Geta issue, 2,7/l, θg, 2, J, 4/7, 2 and 0, 3, 772
．． No. 027, 3. ZaOF, No. 00.3, British Patent/.

Those described in Guzato, No. 997, etc. can be used.

The photographic emulsions used in this invention may be spectrally sensitized with nonane dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemi-,
Cyanine dyes, styryl dyes, and hemioxo/-
JL dyes are included. Particularly useful dyes include cyanine dyes, merocyanine dyes and synthesized merocyanine complexes.
It is a pigment that For these pigments, any of the cyanine pigments and commonly used nuclei can be used as basic heterogeneous nuclei. Namely, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Cedar in which an aromatic hydrocarbon ring is fused to the nucleus, that is, indolenine nucleus, benz/indolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benz imidazole nucleus,
Quinoline nuclei etc. can be applied. These nuclei may be substituted on carbon atoms.

Melonanine dyes or complex merocyanine dyes contain -pyrazoline-! as a core with a ketomethylene structure. -on nucleus, theohydanraincedar, nothiokitizolidine-, goushimene nucleus, thiazolidine-λ, gougeone nucleus,
It can be used for rhodanine nuclei, thiobarbital acid radicals, etc.

Useful sensitizing dyes include, for example, German Patent No. 929, 0? θ
No., U.S. Patent Co., -3/, to! ! Same number.

Geta 3.74tF, same, O03,771, same λ,
3゛/ri, 00! No., λ, 9/, No. 2,329, No. 3
．． ni1<, wow! No. 9, same 3. t72. ．． ! '97 issue, 3,62g, , 2.77, same, 02j, 3
No. 2, No. 522, British Patent/.

2 octopus, j and toto, special public Sho Kugu/gu o3theta, same! This is what was written in No.2 Guzadag.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is the US patent λ
, &J”f, jgu! issue, same.

No. 977.229, 3.397, OAO No. 3
, ! No. 22.052, 3, f27, 77
No. 3. /7. ．． No. 293, 3.62, and No. 9, 3.62. ttl:', No. 41 #0, 3. I! to 72
．． ? 9za issue, same 3. 79. 3,703゜372, 3.7t9.3θ/, 3. i/ri, ni 09, same 3. ! 32. ? 2nd issue, same gu.

021,. No. 702, British Patent/, 3G 41.2 and 7, same/, Δ゛θ7J03, Special Publication No. 3-G 93,
Same, 3-3-/, 2.3? ,! No., JP-A-Shoj, 2-i
10. Same number as ti! 2-/θ9. Ri2! listed in the number.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 933,390, 3. and 3.
! ;, 7.2! 3,31), aromatic organic acid formaldehyde condensates (e.g., U.S. Pat.
0), cadmium salts, azaindene compounds, etc. US Patent 3.1>/! .

73, 3. Otsu is, Zari No. 7, 3,1/7゜29
! No. 3. The binding described in No. 36.727 is particularly useful.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

Specific examples of dyes that can be used include British patents s, s”tit,
t.

No. 2, same/, /77.729, JP-A Akirito-r3/3
No. 0, same 2-29g, No. 20, same getter // ¥ 2θ
Same issue! Ko/θ! , //T issue, US Patent 2. Co7g,
7♂λ No., same J, 333, 417 co No., same, 9
J-Otsu, No. 79, 3. /Riza.

/f7 issue, same 3. /77.07 No. 3. -2 gua,
No. 127, 3. - Tag θ, and No. 27, same 3° No. 2j,
2θgu No. 31, No. 3,90! No. 3.7/Za, 7
2.2 issue, same group, 07/, 3!2 issue, same group, 070,
This was written in No. 3 Oko.

In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a brightening agent such as a stilbene type, triazine type, oxazole type, or certain Ihacmarine type. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion.

Specific examples of fluorescent brighteners are given in U.S. Patent 2. /; 32,7θ/ issue, same 3゜2, ? No. 41O, 3,3! 702, British patent? ! 2.07! No., same/, 3/9.7 Go 3
It is written in the number etc.

When carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example, U.S. Pat. , 3/ri issue, same, x, 7o/, i9Z issue, same, 7θg, 7!3 issue, same 2, 72. ! ? , No. 59, 2.73.2
, No. 300, No. 2,733, 7g No. 5, Same, 710
, Za0! No. 2+za/ni.

No. 02J', British Patent No. 313.92/, etc. Sago or hydroquinone derivatives, U.S. Patent No. 3.4 Tough, No. 079, British Patent No. 3.0 and 9.2 No. 2, etc. Gallic acid derivatives described in US Patent λ, 23! , 7 Otsu! No. 3. 9, No. 909, special public official Shoguji, 20ri No. 77,
The wide range of p-alkoxyphenols described in J-2-A&, No. 23, U.S. Patent No. 3゜4t32, 3θθ, No. 3
, No. 373.050, No. 3,17, No. 22, No. 3,
2g, No. 337, JP-A-32-3J, No. 33, Okoh/G7, No. 3, 3; +2-/! p-oxyphenol derivatives described in 2.2.2j, U.S. Pat.
There are bisphenols described in No. 700°y-ts.

The light-sensitive material produced using the present invention may contain a ha-f-droquinone derivative, an a-minophenol derivative, a gallic acid derivative, an ascorhinic acid derivative, etc. as a color antifogging agent. , 3 to θ, 29θ
No., same co, 33 otsu, 3.2゜7 dragon, same co, g03,72
No. 7, same 2. ri7/to.

t/3 issue, 2.1.7! , No. 3747, 2.70/
, No. 97, No. 2, 20, No. 2/3, same.

7-JF, No. 1.39, No. 2.732.300, Same, 73! , 7 Otsu S issue, JP-A-50-92.9 Zato issue, same, fO-92, 9j? No. 9, J-o-93, 92
L5' issue, 30-/70.337, same! 2-/g to 23! No. Tokko Akira! It is described in θ-, 23, J'/3, etc.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

Any known method can be used for the photographic processing of the light-sensitive material of the present invention. A known treatment liquid can be used. Processing temperature ranges from normal/i0C to rooC
temperature chosen between /er'c or t
The temperature may exceed ooC. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., guamino-N, N-diethylaniline, 3-methyl-guamino-N, N-diethylaniline, quaamino-N-ethyl-he-β). -hydroxyethylaniline, 3-methyl-guamino-he-ethyl-N-β-hydroxyethylaniline, 3-methyl-guamino-N-ethyl-N-
β~notanesulfamide etheraniline, guamino-
3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, Photograph by F.A., Mason
hicProcessing Chemistry (p
221. published by ocal Prese, /9t). ~
229 pages, US Patent Co., /93. θ/! No., same, O9
Those described in No. 2 and 3, JP-A No. 933, etc. may be used.

Color developers may also contain development inhibitors or antifoggants such as alkali metal sulfites, carbonates, borates, and phosphates, buffers, bromides, iodides, and organic antifoggants. can be included. Also, if necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as Hensyl alcohol, diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, compounds, etc. Coupler, fogging agent such as sodium borohydride, auxiliary developer such as phenyl-3-pyrazolidone, viscosity imparting agent, polycarboxylic acid chelating agent described in U.S. Pat. (OLS)
, No. 2,622,9jO, etc. may also be included.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (1) and cobalt (
1), compounds of polyvalent metals such as chromium (Vl) and copper (II), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, iron (
1) or organic complex salts of cobalt (1), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /, 3-diamino-2-propatoltetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid. Complex salts; persulfates, permanganates; nitrosophenols, etc. can be used. Among these, potassium ferricyanide, sodium ethylenediaminetetraacetate iron(1), and ammonium ethylenediaminetetraacetate iron(1) are particularly useful.Ethylenediaminetetraacetate iron(1) complex salts can also be used in independent bleaching solutions. , - Also useful in bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, U.S. Patent 3.0412.5
No. 20, 3.24t/, TDT No., Special Public Shogu 1-/1
The bleaching accelerators described in Japanese Patent Publication No. 0, No. 13, No. 13, etc., can also be obtained.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

Example / Coupler (1) of the present invention/θ, trioctyl phosphate/θmil and ethyl acetate θm,d! The solution obtained by heating to θ0C is gelatin 10? and sodium dodecylbenzenesulfonate o. Aqueous solution l containing 4tt
θθmal=added, stirred, and then passed through a colloid mill for fine ζ-2 emulsion dispersion.

The entire emulsion was added to a photographic emulsion θθ2 containing silver chlorobromide 2/f and gelatin cog f, and after adding 30 ml of a 2% aqueous solution of cycloloader-hydroxytriazine, the pH was adjusted to 1.0. Then, it was applied uniformly onto a triacetic acid fiber film base. This is designated as sample A.

In place of the above coupler (1), coupler (2), (5Lα
A film was prepared using the same molar amount of υ as in (1) and the same procedure. These are designated as samples B, C, and D, respectively.

For comparison, the same mole of the comparative coupler (/θ/) was used in place of the above coupler (1), and a film was prepared by the same procedure. These samples are referred to as E.

〉 (10/) Tokukai Showa J7-/! 72g6 Coupler Description These films were subjected to continuous exposure with a sensitometric wedge and processed as follows.

Process Temperature Time/0 color development 3t0c 3'oo'co. stop
Stop. :zso-3o0C o' yo '3, 1st
Fixation, zt -3o'c o'yo'g. Drifting
White 2t -3o0C /'oo“!.Second
Established. :ts -3o°C o'<to'6, water washing alt'-3'0'CO'30'Here, the composition of each treatment liquid in each treatment step is as follows.

Color developer sodium sulfite s. oy tag-mino-3-methyl-N,N-diethylaniline 3.07 Sodium carbonate -〇. oy potassium bromide
λ. θ7 Add water
/1pH10. s Stop solution sulfuric acid (t N ), t o ,
om71! Add water /
1pHi. .

Fixer ammonium thiosulfate go. θ2 Sodium sulfite 2.01 Sodium hydrogen sulfite /θ. Add water
/lpHo. ? Bleach solution Potassium ferricyanide 3θ, θ7 Potassium bromide /! ．． Add water
/lpH,j When the cyan image of the treated sample was measured, all of them showed a good absorption coefficient in terms of color reproduction.

Each developed film was tested for fastness.

The fastness when the sample was left in the dark at 700°C for 1 day, the fastness when the sample was left in the dark at 7θ%RH for 6 weeks at OoC, and the fastness when the sample was left in the dark at 700°C for 6 weeks, and the fastness in
Table 1 shows the fastness when exposed to daylight as the initial concentration/the rate of decrease in concentration at θ.

From these results, it is clear that the couplers of the present invention have excellent robustness.

Example The following first layer (most layer) on the cellulose cotriacetic acid support ~
The sixth layer (top layer) is applied to the multilayer color photosensitive film (
Sample F) was prepared.

(Table λ*/magenta coupler; 3-'(#2-taloro!-tetradecanamide anilino)-/-(z, g, otsu-1 trichlorophenyl) -2-pyrazoline-!-on*flood capcou solvent; phosphorus Acid resyl ester *3 cyan coupler;, 2-L2-chlorobenzamide) - Guri Roro! - [α-(2-chlorophenoxy)tetradecanamide] Phenol (Kabuku of the present invention, 2) *G coupler solvent; phthalic acid dibutyl ester (0%
), co-4-di-ter t-amylphenol (ri θ)
)-α-(3-Benzol-ethoxyhydanthyl)-cochro-ro! -Dodecyloxycarbonylacetanilide*coupler solvent; phthalic acid diduterester As a comparative sample, Sample G was obtained by replacing the cyan coupler in the third layer of the above sample with an equimolar amount of comparative coupler (10/).

Each sample film was exposed to blue light, green light, and red light through a bicontinuous wedge and subjected to the same treatment as in the previous example.

When the optical density against red light was measured for each of the samples obtained after the treatment, the results shown in Table 7 were obtained.

Table 3 Next, a fastness test was conducted on each developed film.

Fastness when the sample was left in the dark at /θ0C for 3 days, fastness when the sample was left in the dark at 70% RH for g weeks at tθ0C, and 7 in a xenon tester (20,000 lux).
The fastness when exposed to daylight is expressed as the rate of decrease in density at an initial density of 7.0. It looks like a table.

From these results, the coupler of the present invention has good color development (
It is obvious that it exhibits high maximum density, high gamma) and has excellent fastness.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material containing a cyan dye-forming coupler represented by the following general formula [I]. In the formula, R1 represents a hydrogen atom, a halogen atom, a chain alkyl group or an alkoxy group having a carbon number of / - θ, and R2
represents an alkyl group having carbon number/~2o, R3 represents a hydrogen atom, a halogen atom, or an alkyl group, X represents a group that can be separated (-) during oxidative coupling with a developing agent, and n
represents an integer of / or -.